Process of modifying cellulosic textiles with epihalohydrin-triazone reaction products



PROCESS OF MODIFYING CELLULOSIC TEXTILES WITH EPIHALOHYDRlN-TRIAZONE REACTION PRODUCTS William L. Mauldin, Spartanburg, S.C., assignor to Deering Milliken Research Corporation, Spartanburg, S.C., a corporation of Delaware No Drawing. Filed Aug. 21, 1962, Ser. No. 218,456

- 16 Claims. (Cl. 8116.2)

This invention relates to methods for treating cellulosic textile materials to improve certain characteristics thereof, to the textile materials thus obtained and'to novel compounds and compositions.

According to this invention, a cellulosic textile material as defined hereinafter, impregnated with a novel watersoluble reaction product of an epihalohydrin and a dimethylol-hydroxyalkyltriazone as defined hereinafter, is heated under textile resin curing conditions in the presence of an acid acting catalyst, to chemically fix the reaction product to the cellulosic material while the textile material is in a dry, unswollen condition. Preferably, the textile material is then contacted with strong aqueous base to further chemically fix the compound to the cellulosic material while the textile material is in a wet, swollen condition, thereby producing a product having further improved dry and wet resiliency, i.e., wrinkle resistance or recovery in both the wet and dry state. In a further improvement the textile material is contacted with both strong aqueousbase and a wet cross-linking agent.

It is now well known that cellulosic materials can be treated with a textile resin to impart certain minimum care characteristics to fabrics produced from these textile materials. As a result of this textile resin treatment, fabrics having fairly satisfactory dry resiliency, i.e., good dry crease resistance or recovery, are presently being commercially produced in large quantities. It is characteristic of such fabrics, however, that they must normally be drip dried, i.e., hung dripping wet after being washed, if the fabric is to have a semblance of a pressed appearance when dried. The reason for this is that although substantial dry resiliency can be imparted to the fabric, a lesser degree of wet resiliency, i.e., wet crease resistance or recovery, is imparted to the fabric by the resin treatment. It is impractical to attempt to overcome this deficiency by applying more resin as severe embrittlement or weakening of the material results along with other undesirable features such as a harsh, raspy hand and poor comfort values if the material is to be used in a garment.

By the process of this invention, it is now possible to produce fabrics having good wet as well as dry resiliency While at the same time retaining a higher percentage of the strength of the starting textile material than would be achieved with a conventional resin treatment, e.g., employing a known triazone. By this process, fabrics can be produced having at least as good residual strength and substantially better wet resiliency than is obtained by a conventional textile resin treatment. Frequently, fabrics having both increased residual strength and increased wet resiliency and about the same or greater dry resiliency can be obtained. Other properties are enhanced also, e.g., tear strength often is markedly increased over fabrics treated by a typical resin treatment.

It is therefore an object of this invention to provide a United States Patent novel process for the production of textile materials havv See object to provide a novel treatment of textile materials. It is still another object to provide novel textile materials having good dry and wet resiliency. Another object is to provide novel chemically modified textile materials. Still another object is to provide novel compounds and compositions. Other objects will be apparent to those skilled in the art to which this invention pertains.

Textile materials which can be treated according to the process of this invention are those containing cellulosic fibers in which the anhydroglucose units are chemically substantially unmodified. Thus, the term cellulosic textile material when used herein means any textile material comprising fibers within the above definition, e.g., cotton, linen, jute, flax, regenerated cellulose fibers, including viscose rayon, in the form of staple, yarn and fabrics. This invention is directed primarily and preferably to cellulosic textile fabrics, including nonwovens, knitted and preferably woven fabrics. However, the advantages of this invention can be achieved by treating the cellulosic fibers, yarns, or threads employed to produce these fabrics. The thus treated material, when woven or knitted into fabric will produce a fabric having better wet and dry resiliency than identical fabric woven from identical starting but untreated yarn or thread. Moreover, the properties of the staple yarn and thread are modified in a desirable fashion. Satisfactory results can be achieved employing cellulosic materials containing both improved bythis process, preferably those whose cellulosic content of the fabric is substantial, e.g., about 40% or more by weight. As stated above, the invention is primarily directed to fabrics consisting essentially of cellulosic materials, especially cotton. Bleached and usually also commercially mercerized or printed fabric, e.g., printcloth, broadcloth, and oxfordcloth, is usually employed as the starting fabric. Generally, it is preferred to employ starting fabrics having a tensile strength of at least 35 pounds and a tear strength of at least 400 grams in both filling and warp directions.

The tr-i-azones employed to produce the novel triazoneepihalohydrin reaction products are dimethylol-hydroxyalkyl-tr-iazone, dimethylol-hydroxyalkyl-thiotriazone and the water-soluble ethers thereof. These known classes of compounds are prepared by reacting urea or thiourea with formaldehyde and a hydroxyalkylamine in about l;4:1

- with the lower-alkanol, all as is well known in the art.

The epihalohydrins employed to produce the novel triazone-epihalohydrin reaction products are epichlorohydrin, epibromohydrin, l3-methylepichlorohydrin and other substituted epihalohydrins wherein one or more of the hydrogens of epichlorohydrin or epibromohydnin are substituted by a lower-alkyl group, e.g., methyl or ethyl, or an aryl group, e.g., phenyl.

The triazone-epihalohydrins employed in the process of 'thisinvention' may thus be defined as the water-soluble reaction product of an epihalohydrin and a triazone having the formula wherein m is an integer from 2 to 8, preferably 2 to 4, n is an integer from to 4, preferably 0 to 2, and X is oxygen or sulfur, preferably oxygen. These compounds are believed to be the result of the etherification of the hydroxy group of the hydroxyalkyl radical of the triazone by reaction with the epoxy group of the selected epihalohydrin. While this has not been conclusively proven, the resulting compound reacts with the cellulosic material in a typical textile resin fashion, thus indicating that the methylol groups are essentially unchanged. Also, active halogen, which can be titrated with strong base, is present in the triazone-epihalohydrin reaction product and in the cellulosic material which has been cured at an elevated temperature while impregnated with this reaction product and an acid acting textile resin catalyst, thus indicating that it is the epoxy group, rather than the halogen of the epihalohydrin which reacts with the starting triazone. This reactive halogen is chemically fixed to the resulting fabric, before it is contacted with strong base, as evidenced by the fact that it cannot be removed by Washing with plain water.

If the above conclusions are correct, the triazone-epihalohydrin reaction products employed in the novel process have the formula wherein m, n and X have the values given above and R R R R and R are the groups present on the starting epihalohydrin, e.g., hydrogen, lower-alkyl, aryl, and Hal is chlorine or bromine. Examples of such compounds are the reaction product of epichlorohydrin and about a molar equivalent of dimethylol-hydroxyethyltriazone, epichlorohydrin and dimethylol 'y hydroxypropyl-triazone, epichlorohydrin and dimethylol-fi-hydroxypropyl-triazone, epichlorohydrin and dimethylol- 8-hydroxy-a-methylethyltriazone, epichlorohydrin and dimethylol-hydroxyethylthiotriazone, epichlorohydrin and dimethylol-'y-hydroxypropyl-thiotriazone, and the dimethyl and the diethyl ethers of each of the above compounds.

These triazone-epihalohydrin reaction products are prepared by the reaction of the selected triazone (I) with an epihalohydrin. The reaction can be conducted in an inert organic solvent, in water or a lower-alkanol. reaction will occur slowly at room temperature so elevated temperatures are preferred, e.g., 50100 C. The thus obtained product can then be diluted with water to provide the desired solids concentration. This reaction is apparently unique to a triazone having an N-hydroxyalkyl group attached as compounds such as dimethylol-ethyl triazone and ethylene-bis-dimethyloltriazone do not produce a comparable reaction product.

The molar ratio of epihalohydrin to triazone compound used to produce the reaction product employed in the process of this invention, is not critical, but best results are obtained when the molar ratio is about 1:1. The ratio can be varied from as low as 0.1:1 to 2:1 or higher, preferably 0.5:1 to 1.5, and more preferably 0.9:1 to 1.25: 1. If more than a molar equivalent of epihalohydrin is employed, the excess ordinarily can be removed unchanged when the desired reaction is complete.

The amount of selected triazone-epihalohydrin reaction product which should be employed in the process of this invention will depend, of course, upon the amount of dry or Wet crease resistance or resiliency desired in the treated textile material. Generally, from about 2% to about 25%, prefer-ably 3% to 12%, and more preferably about 5% to is employed, calculated on the weight of the The dry textile material. As with conventional triazone treatment, an aqueous solution of the reaction product is ordinarily employed to impregnate the cellulosic material employing the concentration, usually between about 3% and 40%, which will provide the desired pickup on the selected textile material.

The textile resin catalysts employed during the heating step under textile resin curing conditions are a well-known class of compounds and include the acid acting compounds, i.e., those acidic in character under the curing conditions. The most common are the metal salts, e.g., magnesium chloride, zinc nitrate, and-zinc fiuoroborate, and the amine salts, e.g., monoethanolamine hydrochloride and 2 amino 2 methyl propanol nitrate. The amounts of catalyst to be employed are the same as those employed when using the usual textile resins, e.g., up to about 20% by weight of the triazone-epihalohydrin compound employed, With the preferred range being from about 0.5% to about 10%.

Other additives commonly employed when using the usual textile resins can be employed in the process of this invention. to insure uniform and satisfactory wetting out of the fabric. Softeners, e.g., the dispersible polyethylenes, can be added to improve tear strengths when the textile material being treated is fabric.

In carrying out the heating, i.e., curing, step of the process of this invention the cellulosic material, uniformly impregnated with the selected triazone-epihalohydrin reaction product, is heated under textile resin curing conditions in the presence of an acid acting catalyst. Under ordinary conditions, this step employs conditions identical to "that of a conventional 'resin' treatmentf Forexample, the selected reagents can be applied to the textile material by padding, spraying, or applicator roll and then passed through squeeze rolls, if necessary to achieve the desired pickup of the reagents. Curing temperatures between to 200 C., preferably about to C., are employed to chemically fix the reaction product to the textile material. When employing fabric these steps of drying and curing are conducted while the fabric is free from extraneous wrinkles, usually in a smooth, open width condition. Conventional curing equipment is suitable for this operation. For example, when employing a fabric, the reagents can be applied with the usual equipment and then passed through squeeze rolls and dried, e.g., at room temperature or While the fabric passes through a hot air oven or over heated cans. In production it is preferred to conduct the heating operations on fabric in a tenter frame to maintain the desired dimensions.

The thus treated textile material can then be given a thorough wash to remove the catalyst and any unreacted reagents, although such a step is not necessary.

As stated above, some of the advantages of this invention become apparent immediately after the reaction of the reaction product described with the cellulosic textile material under textile resin curing conditions. For example, greater residual strength is maintained in the fabric or an increase of at least one of dry and wet resiliency is observed, compared with an identical treatment employing the comparable triazone compound not reacted with an epihalohydrin. There are, however, reasons for employing the subsequent stepof reacting the thus treated textile material with strong aqueous base. One of these is that an even greater degree of wet resiliency can be obtained after the second step Without materially affecting the residual strength. The permanency of the treatment tends to be improved by the second step. Resistance to chlorine damage is often markedly improved by the second step.

The step of contacting the textile material with strong aqueous base employs conditions generally employed in the textile trade, and the necessary techniques will be apparent to those skilled in the art. For example, impregnating the textile material with the selected reagents can be accomplished in a manner similar to those employed For example, a surfactant can be addedabout 50-90" C. The textile material is then preferably given a thorough wash to remove all reaction products not chemically fixed to the material.

The strong aqueous bases employed in the second step of the preferred process of this invention are those having a pH of at least as a 1% aqueous solution. The bases most commonly employed are the alkali-metal hydroxides, although other compounds such as sodium silicateand trisodium phosphate can also be employed. These bases are usually employed as about 0.2% to about 16% aqueous solutions, preferably about 2% to about 10%. The exact concentration, while not critical, will affect the results obtained. The concentration which gives the optimum result will depend, in part, on the percent pickup of the base by the textile material, the temperature at which the reaction is conducted, and the amount of base consumed in the reaction. Generally, the amount of base applied to the textile material should be at least the amount that will be consumed by the base reactive halogen group present in the triazone-epihalohydrin reaction product. Generally, a 1% to 10% aqueous solution of base is preferred when the wet pickup isbetween about 30% to 130%, calculated on the weight of the dry textile material.

While the wet configurational memory of the cured cellulosic material is improved by contacting it with strong base in the manner described above, even greater increases in wet configurational memory, as well as increases in dry configurational memory, are achieved if the cured material is contacted with both a strong aqueous base as defined above and a wet cross-linking agent, e.g., in the manner described in the application of D. M. Gagarine, S. N. 24,265, now US. Pat. No. 3,175,875, filed April 25, 1960, and in US. 2,985,501. Wet cross-linking agent means a polyfunctional agent which will cross-link the cured cellulosic material While it is in a hydrated state, usually in the presence of less than 130%, preferably less than 100%, e.g., -90%, moisture calculated on the weight of the dry cellulosic material. Wet cross-linking agents within the above general classification can bedivided into three general classes. A first class comprises the polyepoxy cross-linking agents including diepoxybutane; the diglycidyl ether of ethylene glycol, propylene glycol, or diethylene glycol; the triglycidyl ether of glycerol; and the diglycidyl ether of bisphenol A; compounds having an rat-halohydrin group, e.g., chlorohydrin or bromohydrin, in place of one or more of the epoxy groups and compounds having a halogen atom, e.g., chlorine or bromine, on a carbon atom adjacent either an epoxy group or a halohydrin group. Examples of such latter com pounds are epichlorohydrin, 1,3-dichloropropanol-2, 1,3- dib romopropanol-2, and bis-(1-chloro-2-hydroxy-n-propoxy)ethane. A second class of preferred alkaline catalyzed wet cross-linking agents include the sulfone activated divinyl compounds. Examples of this class of compounds are divinyl sulfone, bis-(vinyl sulfonyl) methane, and 1,4- bis-(vinyl sulfonyl)butane. A third class of alkaline catalyzed wet cross-linking agents are the carbonyl activated divinyl compounds, e.g., divinyl ketone, and octa-l,7- diene-3,6-dione. A fourth class are thecarbonyl and sulfonyl activated sulfuric acid and phosphoric acid esters and their alkali-metal salts, e.g., disodium bissulfatoethyl sulfone.

The physical properties of the fabrics treated according to the process of this invention Were determined according to accepted standard methods. Tear strength was determined by A.S.T.M. test designation D-1424-59. Ten- I sile strength was determined by A.S.T.M. test designation D-39-59 (No. 10).

Crease recovery angle was deter- 6 mined by A.S.T.M. test designation D-1295-53T. See A.S.T.M. Standards for Committee D-l3 on Textiles (1959). Flat dry ratings were by A.A.T.C.C. test designation T-88-195 8.

The following is illustrative of the processes and products of this invention, but is not to be construed as limiting.

Example I In a 5 liter round bottom flask fitted with stirrer and condenser place 600 g. (10 moles) urea, 1200 g. (40 moles) of paraformaldehyde and 700 g. of dry methanol. To the stirred mixture slowly add 610 g. (10 moles) of ethanolamine. Stir until the mixture becomes homogeneous and then heat the mixture to 55 C. and add 920 g. (10 moles) of epichlorohydrin at a brisk rate to the thus produced dimethyl ether of dimethylol-hydroxyethyl-triaz'one. Heat the mixture at '80 C. for 3 hours. The thus produced product consists essentially of the dimethyl etherof N-B-hydroxyethyl-dimethylol triazoneepichlorohydrin reaction product, pH 8.5, 68% cup solids, 22.6% water, Brookfield viscosity 130 c.p.s., 1.5 ml. 1 N H to neutrality.

Example II Following the procedure of Example I, the N-B-hydroxyethyl-dimethylol triazone-epichlorohydrin reaction product is prepared by substituting water for the methanol. This compound can also be prepared in a substantially anhydrous condition by removing the water aze'otropically with benzene, followed by removal of the benzene prior to the addition of the epichlorohydrin. However, care must be exercised to prevent overheating during reaction with resulting product decomposition.

Example III Following the procedure of Example I, the dimethyl ether of N-B-hydroxyethyl-dimethylol thiotriazone-epichlorohydrin reaction product is prepared by substituting an equimolar amount of thiourea for the urea.

Any, or any combination of the following variations in the procedure of Example I can also be employed:

(a) The methanol can be replaced by ethanol, propanel or butanol;

(b) The amount of epichlorohydrin can be varied from 0.1.to 1.5 molar equivalents;

(c) The epichlorohydrin can be replaced by epibromohydrin or ,B-methylepichlorohydrin;

(d) The ethanolamine can be replaced by an equimolar amount of 2-aminopropanol or 3-aminopropanol.

Example IV Pass 39" 80 x 80 4.00 yd./lb. (in the greige) bleached and mercerized printcloth having 45 lbs. tensile and 450 g. tear (filling) into a pad bath containing either 10% dimethylol-hydroxyethyl triazone (Rhonite N-17, Rohm & Haas, assuming 50% solids) or 15% of a triazone-epichlorohydrin reactant .prepared in the manner of Example I using a 1:4:2.2:1:l ratio of urea, paraformaldehyde, methyl alcohol, monoethanolamine and epichlorohydrin (equivalent to about 10% dimethylol-hydroxyethyl triazone) 1.5% Zn(NO -6H O, 2.5% formalin (to insure an excess of formaldehyde) and 0.35% Surfonic N- wetting agent. Adjust pickup to about 70%. Dry the fabric and cure in an oven at 350 F. for 1.5 minutes. Wash thoroughly.

Fabrics thus treated were found to have the properties shown in Table I.

7 Example V Pad fabrics obtained according to the procedure of Example IV (without washing) with aqueous KOH. Adjust wet pickup to about 70-75%. Roll up in a 8 By comparing Sample 4 with 3 and 1, 8 with 7 and 5, 12 with 11 and 9, 16 with 15 and 13, 20 with 19 and 17, and 24 with 23 and 21, it can be seen that when fabric treated with the triazone-epichlorohydrin reactant f-olsmooth roll, encase in a polyethylene bag and maintain 5 ig gfi g gig j' 2312 2 igi ig i ii z fiifi f z fifi at room temperature for 30 minutes. Wash the fabric i p S S 1 v azone, with or without the second NaOH-ep1 treatment, thoroughly. Fabrics thus treated were found to have the m erties shown in Table H the trlazone-epichlorohydnn treated fabric w1ll have sub- P p stantially better spin performance than the triazone treated TABLE II fabric. Conversely, if about the same spin performance is achieved in the two types of fabrics, the triazone-epi- Reawmt Spin Tumble 21g? chlorohydrin treated fabric will have substantially higher (1m) tensile and tear strength.

Exam le VII N-l7 3.0 3.4 29 220 p Triazone-epi 4. 3 5. 0 27 240 Follow the procedure of Example VI, but substitute the dimethyl0l-hydroxyethyl-triaz0ne epichlorohydrin reac- E l V1 tion product produced according to the procedure of Example II for the corresponding dimethyl ether employed a S 3 235 23 12; 23 ggfilr ggg in Example VI. The thus obtained fabric has substan- 11 me I P c 1 g 1 tially the same properties as that obtained according to tear (fillmg) 1nto a pad both conta1n1ng either 5% or 10% the procedure of Example IV solids (calculated on the basis of the starting hydroxyethyl triazone) of the triazone-epichlorohydrin reaction Example VIII Product of EXample 0T 5% 10% of dlmet'hylol' Follow the procedure of Example VI but substitute the h d th l-tr'azo e (Rhon'te N-l7 Roh & Haas 1 J y YQ Y 1 1 2 m t dimethyl ether of N-fl-hydroxyethyl-d1methyl-ol-th1otri- 0% SOIIdS assumed 111 the Commercial P In each azone-epichlorohydrin reaction product obtained accordcase P 11/2% or 3)2 2 catalyst ing to the procedure of Example III. Fabric thus oband 4% p emulsified Polyethylene softener, tained has substantially the same properties as that ohand sufiicient acetic acid to bring the pH of the bath to tain d according to the procedure of Example I. a u J Wet P p t0 filbollt (The It has been noted that fabrics treated with a reactant of percent of triazone-eplchlorohydrln rea a t was calcuthis invention has a tendency to pick up soil when washed lated on the bas1s of the startmg triazone, rather than ith yery di t t i l s g i m hi tendencycan the product so that the compans'on'would'be on a molar b virtually eliminated if the fabric is impregnated with a rather than Weight basls.) Dry the 1mpregnated fabrlc sulfonic acid, preferably an aromatic mono or poly sul- 011 y Cans heated W swam at 17 P- f then Cure fonic acid. For example, fabric obtained following the at 350 F. for 1.5 m1nutes. Impregnate portlons of each procedure of Example VI showed a pronounced tendency of the thus treated fabrics with 2.5% aqu ous N H to pick up soil from dirty water. However, if the fabric Wlth a Wet P p 0f abPut 70%, fPUOWBd y about an is padded with, e.g., a l-10% aqueous solution of Erional 8 to 12% add-on of eplchlorohydrm, calculated on the N. W., the mixed condensation product of naphthalene dry weight of the fabric, apphed by means of an apphsulfonic acid, dihydroxy-diphenyl sulfones and formaldecator roll. Roll up the wet fabr1c on rolls and wrap hyde, and then heated, preferably at a temperature of at in p y y film and then age for two hours at 1 least F., this tendency is substantially eliminated. F. Give all fabric samples a standard Wash w1th deter- Other compounds which can 'be used are the sulfonic acid gent in an automatic washer and dry. 45 group containing synthetic tanning agents, e.g., the con- Fabric thus treated was submitted for testing. The densation product formaldehyde and naphthalene sulfonic results of these tests are shown in Table III. acid, formaldehyde and phenol sulfonic acid, formalde- TABLE III 5% reactant pickup 10% reactant pickup* Before or fter Roactant $23314 szgfilfle Filling r111 g 8%) Filling I F 111 i In Spin Tumble teal. (g) pin Tumble tgigssige i 2 350 Cure, 1% Catalyst Triazone 1 3. 4 3. 9 23. 3 407 5 3. 5 5. 0 2'5. 3 340 Triazone-ep 2 2. 5 3. 4 31. 5 413 6 3. 0 4. 4 31. 5 447 Triazone 3 3. 9 4. 3 23. 5 367 7 3. s 4. 8 24. 0 310 Triazone-epi 4 4. 5 4. 0 25. 0 373 s 3.7 4. 5 30. 2 330 350 Cure, 1.5% Catalyst Triazone. 9 2. s 3. s 27. 7 400 13 3. 7 4. 9 23. 5 333 Triazone-ep 10 3. 2 3. 6 29. 3 413 14 2. 7 4. 4 32 440 Triazone- 11 4. 1 4. 0 23. 3 340 15 4. 9 5. 0 21. 7 300 Triazone-cpi 1 4. 6 4. 1 1. 8 320 16 4. 3 4. 6 26. 7 347 350 Cure, 2% Catalyst Triazone 17 2. 3 3- 7 4- 360 21 3. 8 4. 7 26. 0 310 Triazone-epi 18 3. 4 4. :5 23.8 367 22 2. 0 4. 3 26. 5 427 Triazone 19 3. 7 4. 1 22. 0 327 23 4. 0 5. 0 24. s 330 ,Triazone-epi 20 4. 1 4. 5 25. 3 360 24 4. a 4. 6 27.8 360 .*The percent of triazone-epichlorohydrin reactant was calculated on the basis of the starting trlazone reactant.

groups per anhydroglucose unit which comprises curing said material, impregnated with a water-soluble reaction product of an epihalohydrin and a triazone having the formula CmHmirO H wherein m is an integer from 2 to 8, inclusive, n is an integer from to 4, inclusive, and X is selected from the group consisting of oxygen and sulfur, at an elevated temperature in the presence of an acid acting catalyst, and then contacting the material with a strong base under aqueous conditions until reaction with the base reactive halogens on said material is substantially complete.

2. A method according to claim 1 wherein the epihalohydrin is epichlorohydrin.

3. A method according to claim 1 wherein X is oxygen and m is 2.

4. A method according to claim 1,wherein the cellulosic material is cotton fabric.

5. A method according to claim 1 wherein a wet cross linking agent is applied to the material along with the strong base.

6. A method according to claim 5 wherein the wet cross-linking agent is epichlorohydrin.

7. A method for improving the properties of a cellulosic textile fabric whose cellulosic content contains at least 1.8 free hydroxy groups per anhydroglucose unit which comprises the steps of applying to said fabric a water-soluble reaction product of between about 0.1 and about 1.5 moles of epichlorohydrin and a hydroxyethyl triazone having the formula wherein n is an integer from 0 to 2, inclusive, curing said reaction product on said fabric at an elevated temperature in the presence of an acid acting catalyst, and thereafter applying an aqueous solution of at least a molar I equivalent, calculated on the reaction product, of an alkalimetal hydroxide to the resulting fabric until reaction with the base reactive halogens on said fabric is substantially complete.

8. A method according to claim 7 wherein the fabric is cotton.

9. A method according to claim 7 wherein the reaction product is that of about one molar equivalent of epichlorohydrin and triazone are utilized, and wherein n is 1.

10. A method according to claim 7 wherein the reaction product is that of about one molar equivalent of epichlorohydrin and triazone are utilized, and wherein n is 0.

11. A method according to claim 8 wherein a wet crosslinking agent is applied to fabric along with the strong base.

12. A method according to claim 11 wherein wet crosslinking agent is epichlorohydrin.

13. A method for improving the properties of a cellulosic textile material containing at least 1.8 free hydroxy groups per anhydroglucose unit which comprises curing said material, impregnated with a water-soluble reaction product of an epihalohydrin and a triazone having the formula (O uHin+i) 0 0 H2-N C H mOH wherein m is an integer from 2 to 8, inclusive, n is an integer from 0 to 4, inclusive, and X is selected from the group consisting of oxygen and sulfur, at an elevated temperature in the presence of an acid acting catalyst. 14. The product of the method of claim 13. 15. The product of the method of claim 1. 16. The product of the method of claim 7.

References Cited by the Examiner 1 UNITED STATES PATENTS 2,615,888 10/1952 Zerner 260-248 2,892,674 6/1959 Sause 8116.2 2,950,553 8/1960 Hurwitz 8-116.3 2,985,501 5/1961 Gagarine 8120 3,014,907 12/1961 Kober 260-248 3,016,281 l/1962 Kropa 8-116.2 3,053,798 9/1962 DAlelio 260-248 NORMAN G. TORCHIN, Primary Examiner.

JULIAN S. LEVITT, Examiner.

I. CANNON,. Assistant Examiner. 

1. A METHOD FOR IMPROVING THE PROPERTIES OF A CELLULOSIC TEXILE MATERIAL CONTAINING AT LEAST 1.8 FREE HYDROXY GROUPS PER ANHYDROGLUCOSE UNIT WHICH COMPRISES CURING SAID MATERIAL, IMPREGNATED WITH A WATER-SOLUBLE REACTION PRODUCT OF AN EPIHALOHYDRIN AND A TRIAZONE HAVING THE FORMULA 